CN109836370A - The synthetic method of the 2,2,6,6- tetramethyl piperidine amine of specific pH range - Google Patents
The synthetic method of the 2,2,6,6- tetramethyl piperidine amine of specific pH range Download PDFInfo
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- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000010189 synthetic method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 5
- 238000004821 distillation Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 5
- 150000004692 metal hydroxides Chemical class 0.000 claims description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims 1
- LWMPFIOTEAXAGV-UHFFFAOYSA-N piperidin-1-amine Chemical compound NN1CCCCC1 LWMPFIOTEAXAGV-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- GDJQNGMJGMABLV-UHFFFAOYSA-N 1,3,3,4-tetramethylpiperidin-2-one Chemical compound CC1CCN(C)C(=O)C1(C)C GDJQNGMJGMABLV-UHFFFAOYSA-N 0.000 abstract description 8
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 abstract description 3
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical compound CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- UFCONGYNRWGVGH-UHFFFAOYSA-N 1-hydroxy-2,2,3,3-tetramethylpiperidine Chemical compound CC1(C)CCCN(O)C1(C)C UFCONGYNRWGVGH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- -1 phenylpiperidines amine Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical compound CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 description 1
- 101000878457 Macrocallista nimbosa FMRFamide Proteins 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical class O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The invention discloses the 2,2,6 of a kind of specific pH range, the synthetic method of 6- tetramethyl piperidine amine, the following steps are included: with 2,2,6,6- tetramethylpiperidone is raw material, raw material and ammonium hydroxide are added in autoclave, first adjusts pH=12.0~13.0, temperature, the setup pressure value of 1.5~2.5Mpa progress hydrogenation reaction of the skeleton nickel as catalyst in 55~65 DEG C is then added, until reaction was completed after pressure is not less than the 2% of setup pressure value always in kettle in continuous 1 hour；The air-distillation of reaction solution elder generation, then rectification under vacuum is carried out, obtain 2,2,6,6- tetramethyl -4- amino piperidine of product.Method of the invention improves the conversion ratio of tetramethylpiperidone, improves product yield.
Description
Technical field
The invention belongs to chemical fields, and in particular to 2,2,6,6- tetramethyl piperidine amine synthetic methods of specific pH range.
Background technique
2,2,6,6- tetramethyl piperidine amine, structural formula such as following formula 1, molecular formula C9H10N2.English abbreviation TAD, Chinese is referred to as
Tetramethyl piperidine amine is to be mainly used for synthesizing bonding type and polymer electrolyte hindered amine light stabilizer one is important chemical intermediate
Agent.
The current synthetic method in relation to 2,2,6,6- tetramethyl piperidine amine has following several:
1. synthesizing tetramethyl piperidine amine using Study on Catalytic Amination of Alcohols method.Document (University Of Tianjin's journal, 1999 (04): 96-99) mentions
The suitable process conditions of Study on Catalytic Amination of Alcohols method out, with tetramethylpiperidone (2,2,6,6- tetramethylpiperidone) and ammonium hydroxide as former
Material, using skeleton nickel as catalyst, is passed through hydrogen at high temperature under high pressure and is reacted.Ammonia and tetramethylpiperidone molar ratio 5:1,
115 DEG C of reaction temperature, reaction pressure 2.5MPa, catalyst amount 20%, tetramethyl piperidine amine actual recovery 82%.This method is anti-
Answer temperature higher, and catalyst amount is big, by-product is more.
In this method, if catalyst amount (such as being reduced to 5%) is reduced, or reduction reaction temperature (such as reaction temperature
Degree is 65 DEG C), resulting yield will be greatly reduced.
2. document (chemical industry and engineering, 2006 (04): 323-326) proposes, using skeleton cobalt as catalyst, four are used
Methylpiperidone synthesizes tetramethyl piperidine amine as solvent as raw material, ammonium hydroxide.90-100 DEG C of reaction temperature, reaction pressure
1.5MPa-2.5MPa, ammonia and tetramethylpiperidone molar ratio 3:1, catalyst amount 10%, tetramethyl piperidine amine selectivity
98%, actual recovery 85% or so.The Co catalysts Costco Wholesale that this method uses is higher, and reaction temperature is high, and energy consumption is high.
3. document (Chemischer Informationsdienst, 1981,12 (21)) propose using electrochemical process into
Row prepares tetramethyl piperidine amine, using tetramethylpiperidone as raw material, is reacted in strong acid media, is carried out on cathode material
Reduction obtains tetramethyl piperidine amine, reacts at 20-55 DEG C, product yield is up to 93-99%.This method uses alkali in cathodic region
Metal phosphate is medium, and anode region electrolyte is 20% sulfuric acid, and aluminium is cathode, and lead is anode.Use strong acid as electrolyte,
It is big to equipment corrosion, it is at high cost, do not meet green chemical concept.
The reason that above-mentioned existing production tetramethyl piperidine amine technical process energy consumption is larger, economic cost is high is not adjust
The pH value of good reaction system causes reaction temperature high, and energy consumption is high.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of 2,2,6,6- tetramethyls of specific pH range that can improve yield
The synthetic method of phenylpiperidines amine.
In order to solve the above technical problem, the present invention provides a kind of 2,2,6,6- tetramethyl piperidine amine of specific pH range
Synthetic method, comprising the following steps:
1), with 2,2,6,6- tetramethylpiperidones for raw material, raw material and ammonium hydroxide is added in autoclave, first adjusts pH=
12.0~13.0, the skeleton nickel as catalyst is then added in 55~65 DEG C of temperature, the setup pressure value of 1.5~2.5Mpa
Hydrogenation reaction is carried out, until (that is, pressure begins in kettle after pressure is not less than the 2% of setup pressure value always in kettle in continuous 1 hour
Remain unchanged eventually), reaction was completed；
The molar ratio of 2,2,6,6- tetramethylpiperidones and ammonia is 1:3.4~3.5, and catalyst charge is material quality
(5 ± 1) %wt；
Illustrate: the ammonium hydroxide of 35~70ml of raw material adapted of every 10g；Therefore, when use when use mass concentration for 25%~
When 28% industrial ammonia, raw material, water and industrial ammonia are added in autoclave, 30 ± 10ml's of raw material adapted of every 10g
Water；
2), the resulting reaction solution elder generation air-distillation of step 1) (to steam isopropylamine, ammonia, these light components such as water), then
It carries out rectification under vacuum (2.6kpa), obtains 2,2,6,6- tetramethyl -4- amino piperidine of product.
The improvement of the synthetic method of 2,2,6,6- tetramethyl piperidine amine as specific pH range of the invention:
After the hydrogenation reaction of step 1), the reaction solution in kettle is taken out, the residue for remaining in bottom is washed, from
And realize the recycling of catalyst.
Note: washing residue to cleaning solution is neutral (that is, pH ≈ 7), obtains reusable catalyst backbone nickel.
The further improvement of the synthetic method of 2,2,6, the 6- tetramethyl piperidine amine as specific pH range of the invention, it is described
Step 1) are as follows: raw material and ammonium hydroxide are added in autoclave, the skeleton nickel as catalyst is added after adjusting pH=12.0~13.0,
First controlling the Hydrogen Vapor Pressure in autoclave is that 0~0.1Mpa (is first passed through air in nitrogen displacement kettle, after nitrogen displacement, then is passed through
Nitrogen in hydrogen displacement kettle, so that pressure is 0~0.1Mpa in kettle), 2 ± 0.5h is stirred to react in 55~65 DEG C；It then proceedes to
Hydrogen is passed through into kettle until pressure reaches that be kept the temperature (55~65 DEG C) after the setup pressure value of 1.5~2.5Mpa anti-in kettle
Answer, when in kettle hydrogen drop to≤setup pressure value 60% after, continue to be passed through hydrogen until pressure reverts to setting pressure in kettle
Force value repeats aforesaid operations, until terminating anti-after pressure is not less than the 2% of setup pressure value always in kettle in continuous 1 hour
It answers.
The further improvement of the synthetic method of 2,2,6, the 6- tetramethyl piperidine amine as specific pH range of the invention utilizes
Metal hydroxides carries out pH adjusting.The metal hydroxides is sodium hydroxide or potassium hydroxide.
The further improvement of the synthetic method of 2,2,6, the 6- tetramethyl piperidine amine as specific pH range of the invention, skeleton
Nickel is Raney Ni catalyst (An Naiji brand, 50 μm of partial size, water seal).
PH value of the present invention by control reaction system, Optimizing Technical, to achieve the purpose that improve yield.
For the present invention in feeding stage, adjusting the pH of reaction system at room temperature is 12.0-13.0, the adjusting of pH by ammonium hydroxide and
Metal hydroxides codetermines.The system pH adjusted is more advantageous to the formation of reaction imines early period, to be conducive to lead
Reaction carries out.Alkalinity is too strong, will lead to tetramethylpiperidone open loop, the excessively weak production for leading to by-product tetramethylpiperidinol of alkalinity
It is raw.
The synthetic reaction equation of 2,2,6,6- tetramethyl -4- amino piperidine of the invention is as follows:
The present invention has following technical advantage:
(1) reaction temperature is reduced, tetramethylpiperidone open-loop products are reduced, improves the selection of tetramethyl piperidine amine
Property.So that reaction condition is milder, the energy consumption cost in reaction process is reduced, the theory of energy-saving and emission-reduction is met.
(2) regulation system pH value can promote the generation of imines, improve the conversion ratio of tetramethylpiperidone, improve
Product yield.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 is that (wherein the peak A be solvent peak isopropanol, and the peak B is tetramethyl for gas chromatogram after the concentration of 1 reaction solution of embodiment
Phenylpiperidines amine, the peak C are by-product tetramethylpiperidinol)；
Fig. 2 is that the mass spectrogram of the peak B product tetramethyl piperidine amine and standard mass spectrogram compare；
Fig. 3 is the structural formula of product tetramethyl piperidine amine.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This.
The testing conditions that following embodiment uses: Agilent 1790F hydrogen flame detector, 30m long SE54 capillary chromatography
Column, nitrogen pressure 100kPa, air pressure 30Pa, Hydrogen Vapor Pressure 100kPa, 260 DEG C of injector temperature, 100 DEG C of initial temperature, just
Begin time 2min, detects 260 DEG C of temperature, 6 DEG C/min of heating rate, 260 DEG C of final temperature.
After GC-MS is detected, 2,2,6,6- tetramethyl piperidine amine of gained, as described in FIG. 1 to FIG. 3.
Skeletal nickel catalyst used in the present invention is the Raney Ni catalyst of commercially available An Naiji brand, 50 μ of partial size
M, water seal.
It in the present invention, not yet explicitly informs, is to carry out at room temperature.
Embodiment 1, a kind of synthetic method of 2,2,6,6- tetramethyl piperidine amine of specific pH range successively carry out following step
It is rapid:
(1) 30ml water, 2,2,6,6- tetramethylpiperidone 10g (0.0644mol) of raw material, quality point are added into autoclave
NaOH about 0.05g is added in the ammonium hydroxide 15g (ammonia 0.22mol) that number is 25%, thus pH value=12.0 of regulation system, then plus
Enter 0.5g skeleton nickel as catalyst.
(2) it is passed through air in nitrogen displacement kettle, after nitrogen displacement, then is passed through nitrogen in hydrogen displacement kettle, at this time kettle internal pressure
Power is 0Mpa.Stirring and heating device are opened, material in kettle is made to be increased to 60 DEG C, 400 revs/min of speed of agitator.
(3) after stirring 2h, start to be passed through hydrogen to pressure into kettle to be 2.5MPa, heat preservation is reacted；When hydrogen in kettle
Drop to≤1.5MPa after, continue to be passed through hydrogen until pressure is 2.5MPa in kettle, this operation repeated, until in continuous 1 hour
Pressure is not less than 2.45Mpa always in kettle, and reaction terminates.
(4), after above-mentioned hydrogenation reaction, the reaction solution in kettle is taken out, the residue for remaining in bottom is washed, it is residual
Pulp water is washed till cleaning solution as neutral (that is, pH ≈ 7), obtains reusable catalyst backbone nickel；To realize returning for catalyst
It receives.
By the air-distillation of reaction solution elder generation (thus steaming these light components such as isopropylamine, ammonia, water), then rectification under vacuum is carried out,
Component at 103 DEG C of 2.6kpa temperature of collection, obtains 2 as product, 2,6,6- tetramethyl -4- amino piperidines, yield is
95.3%, purity 99.5%.
Embodiment 2 " addition NaOH about 0.05g " will be changed to that " NaOH about 0.1g " is added in embodiment 1, at this time the pH of system
It is 12.7, remaining is equal to embodiment 1.Product yield is 96.2%, purity 99.1%.
Illustrate: suitably increasing a small amount of NaOH again, so that the pH of regulation system is 13；Remaining is the same as above-described embodiment 2；Gained
The yield and purity of product are substantially the same as embodiment 2.
Embodiment 3 " will make material in kettle be increased to 60 DEG C " to be changed to " increasing temperature to 55 DEG C " in embodiment 1.Remaining etc.
It is same as embodiment 1.
Product yield is 96.1%, purity 99.1%.
Embodiment 4 " will make material in kettle be increased to 60 DEG C " to be changed to " increasing temperature to 65 DEG C " in embodiment 1.Remaining etc.
It is same as embodiment 1.
Product yield is 96.1%, purity 99.2%.
The step 3) of embodiment 1 is changed to by embodiment 5: after stirring 2h, being started the hydrogen for being passed through 2.0MPa into kettle, is protected
Temperature is reacted；When in kettle hydrogen drop to≤1.2MPa after, continue to be passed through hydrogen until pressure is 2.0MPa in kettle, repeat this
Operation, until pressure is not less than 1.96Mpa always in kettle in continuous 1 hour, reaction terminates.That is, setup pressure value is by 2.5Mpa
It is changed to 2.0Mpa.Remaining is equal to embodiment 1.
Product yield is 94.7%, purity 99.2%.
" NaOH about 0.05g will be added, so that the pH value 12.0 " of regulation system is changed to " addition in step 1) in embodiment 6
KOH about 0.02g, thus the pH value 12.0 " of regulation system remaining be equal to embodiment 1.
Product yield is 95.2%, purity 99.1%.
Embodiment 7, the catalyst using recycling:
Resulting catalyst backbone nickel substitution skeleton nickel is recycled with embodiment 1, dosage is constant；Remaining is equal to embodiment 1.
Product yield 95.2%, purity 99.3%.
Comparative example 1, the use for cancelling catalyst；That is, being changed to " be added without by " NaOH about 0.05g being added " in embodiment 1
NaOH ", the pH of system is 11.7 at this time, remaining is equal to embodiment 1.
Product yield is 72%, purity 92.2%.
Comparative example 2 " addition NaOH about 0.05g " will be changed to " NaOH about 0.5g is added " in embodiment 1, at this time the pH of system
It is 14, remaining is equal to embodiment 1.
Product yield 61%, purity 89.1%.
Comparative example 3 " will be added water 30ml, the ammonium hydroxide 15g that mass fraction is 25% be added, NaOH is added about in embodiment 1
0.05g " be changed to " be added water 40ml, be added mass fraction be 25% ammonium hydroxide 10g (ammonia 0.147mol), be added without NaOH ",
The pH of system is 10.9 at this time, remaining is equal to embodiment 1.
Product yield 65%, purity 91.5%.
The step 1) of embodiment 1 is changed to by comparative example 4: 30ml water, 2,2,6,6- tetramethyl of raw material being added into autoclave
Piperidones 10g, the ammonium hydroxide about 25g that mass fraction is 25% add 0.5g skeleton nickel conduct to make the pH value 12.0 of system
Catalyst.Remaining content is equal to embodiment 1.
Product yield is 87%, purity 90%.
Comparative example 5 " will make material in kettle be increased to 60 DEG C " to be changed to " increasing temperature to 45 DEG C " in embodiment 1.Remaining etc.
It is same as embodiment 1.
Product yield is 51%, purity 75%.
The step 3) of embodiment 1 is changed to by comparative example 6:
After stirring 2h, start the hydrogen that 1.3MPa is passed through into kettle, heat preservation is reacted；When in kettle hydrogen drop to≤
After 0.78MPa, continue to be passed through hydrogen until pressure is 1.3MPa in kettle, repeat this operation, until pressure in kettle in continuous 1 hour
Always it is not less than 1.274Mpa, reaction terminates.That is, setup pressure value is changed to 1.3MPa by 2.5Mpa.Remaining is equal to embodiment
1。
Product yield is 42%, purity 48%.
" stirring 2h " in comparative example 7, cancellation step (3) before being passed through the hydrogen of 2.5MPa；I.e. are as follows: step 2) heating
Afterwards, the hydrogen of 2.5MPa is directly passed through into kettle, heat preservation is reacted；Remaining content is equal to embodiment 1.
Product yield is 66%, purity 75%.
Skeleton nickel dosage as catalyst is changed to 2g by 0.5g by comparative example 8, remaining content is equal to embodiment 1.
Product yield and purity are substantially the same as embodiment 1.That is, the dosage for increasing catalyst not can increase product yield.
The above list is only a few specific embodiments of the present invention for finally, it should also be noted that.Obviously, this hair
Bright to be not limited to above embodiments, acceptable there are many deformations.Those skilled in the art can be from present disclosure
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (6)
1. the synthetic method of 2,2,6,6- tetramethyl piperidine amine of specific pH range, it is characterised in that the following steps are included:
1), with 2,2,6,6- tetramethylpiperidones for raw material, raw material and ammonium hydroxide are added in autoclave, first adjust pH=12.0~
13.0, it is then added and is added as the skeleton nickel of catalyst in 55~65 DEG C of temperature, the setup pressure value of 1.5~2.5Mpa
Hydrogen reaction, until reaction was completed after pressure is not less than the 2% of setup pressure value always in kettle in continuous 1 hour；
The molar ratio of 2,2,6,6- tetramethylpiperidones and ammonia be 1:3.4~3.5, catalyst charge be material quality (5 ±
1) %；
2), the resulting reaction solution elder generation air-distillation of step 1), then rectification under vacuum is carried out, obtain 2,2,6,6- tetramethyl -4- of product
Amino piperidine.
2. the synthetic method of 2,2,6,6- tetramethyl piperidine amine of specific pH range according to claim 1, it is characterised in that:
After the hydrogenation reaction of step 1), the reaction solution in kettle is taken out, the residue for remaining in bottom is washed, urged to realize
The recycling of agent.
3. the synthetic method of 2,2,6,6- tetramethyl piperidine amine of specific pH range according to claim 1 or 2, feature exist
In:
The step 1) are as follows: raw material and ammonium hydroxide are added in autoclave, is added after adjusting pH=12.0~13.0 as catalyst
Skeleton nickel, first control autoclave in Hydrogen Vapor Pressure be 0~0.1Mpa, be stirred to react 2 ± 0.5h in 55~65 DEG C；Then after
Continue and is passed through hydrogen into kettle until pressure carries out insulation reaction after reaching the setup pressure value of 1.5~2.5Mpa in kettle, when in kettle
Hydrogen drops to≤setup pressure value 60% after, continue to be passed through hydrogen until pressure reverts to setup pressure value in kettle, repeat
Aforesaid operations, until reaction was completed after pressure is not less than the 2% of setup pressure value always in kettle in continuous 1 hour.
4. the synthetic method of 2,2,6,6- tetramethyl piperidine amine of specific pH range according to claim 3, it is characterised in that:
PH adjusting is carried out using metal hydroxides.
5. the synthetic method of 2,2,6,6- tetramethyl piperidine amine of specific pH range according to claim 4, it is characterised in that:
The metal hydroxides is sodium hydroxide or potassium hydroxide.
6. the synthetic method of 2,2,6,6- tetramethyl piperidine amine of any specific pH range according to claim 1~5, special
Sign is: skeleton nickel is Raney Ni catalyst.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN110642776A (en) * | 2019-10-29 | 2020-01-03 | 南京工业大学 | Process for catalytically synthesizing 2,2,6, 6-tetramethyl-4-aminopiperidine |
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| CN110317162A (en) * | 2019-07-26 | 2019-10-11 | 宿迁联盛科技股份有限公司 | Tetramethyl piperidine amine is continuously synthesizing to method and synthesizer |
| CN110642776A (en) * | 2019-10-29 | 2020-01-03 | 南京工业大学 | Process for catalytically synthesizing 2,2,6, 6-tetramethyl-4-aminopiperidine |
| CN110642776B (en) * | 2019-10-29 | 2022-04-26 | 南京工业大学 | Process for catalytically synthesizing 2,2,6, 6-tetramethyl-4-aminopiperidine |
| CN111100331A (en) * | 2019-12-20 | 2020-05-05 | 宿迁联盛科技股份有限公司 | Light stabilizer and preparation method and application thereof |
| CN111100331B (en) * | 2019-12-20 | 2021-11-16 | 宿迁联盛科技股份有限公司 | Light stabilizer and preparation method and application thereof |
| CN111233749A (en) * | 2020-03-30 | 2020-06-05 | 利安隆凯亚(河北)新材料有限公司 | Pretreatment method of tetramethyl piperidone and synthesis method of tetramethyl piperidamine |
| CN111233749B (en) * | 2020-03-30 | 2021-07-02 | 利安隆凯亚(河北)新材料有限公司 | Pretreatment method of tetramethyl piperidone and synthesis method of tetramethyl piperidamine |
| CN111689893A (en) * | 2020-07-08 | 2020-09-22 | 江苏富比亚化学品有限公司 | Preparation method of 2,2,6, 6-tetramethyl-4-aminopiperidine |
| CN111689893B (en) * | 2020-07-08 | 2021-08-31 | 江苏富比亚化学品有限公司 | Preparation method of 2,2,6, 6-tetramethyl-4-aminopiperidine |
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